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Catalyst Design Based on Functionalized Phosphines with a Compact Coordination Center

基于具有紧凑配位中心的功能化膦的催化剂设计

基本信息

批准号：
18350047
负责人：
SAWAMURA Masaya
金额：
$ 11.29万
依托单位：
Hokkaido Univesity
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

1. Research with Caged Phosphine SMAPThe procedure for the synthesis of Ph-SMAP, the parent compound for various SMAP derivatives, was improved. It was confirmed that Ph-SMAP is an excellent ligand for hydrosilylation and hydrgenation of ketones.SMAP was immobilized on silica gel surface. Silica-SMAP thus obtained showed very high ligand performance for the Rh-catalyzed hydrosilylation and hydrogenation of sterically demanding ketones.Furthermore, Silica-SMAP was successfully used for the development of Ir-catalyzed directed ortho borylation of functionalized arenes.SMAP derivatives bearing an alkanethiol pendant at the bridgehead silicon atom was prepared and used for the preparation of self-assembled monolayer on gold surface. Au-SMAP thus prepared showed remarkably high activity and turnover efficiency in the Rh-catalyzed dehydrogenative alcohol silylation.2. Research with Semihollow TrialkynylphosphinesTriethynylphosphine ligands with different end-cap groups were synthesized. Those with bulky end-caps showed unique coordination properties to form 1:1 metal-phosphine complexes selectively with various transition metal species. The semihollow-shaped triethynylphosphines showed extraordinally high accelerating effect in the Rh-catalyzed hydrosilylation of ketones. Furthermore, the semihollow triethynylphosphines were successfully used as ligands for gold-catalyzed alkyne cyclizations. In particular, the accelerating effect in the 6-exo-dig and 7-exo-dig cyclization was remarkable. In addition, this catalyst system enabled unprecedented cyclizations of internal alkyne derivatives.

1.笼状膦SMAP的研究改进了SMAP衍生物的母体Ph-SMAP的合成方法。研究表明，Ph-SMAP是一种优良的酮硅氢加成和氢化反应配体。SiO_2-SMAP在铑催化的硅氢加成反应和酮的氢化反应中表现出很好的配体性能，并成功地应用于铱催化的芳烃的邻位硼化反应，制备了在桥头硅原子上带有烷基乙撑基的SMAP衍生物，并用于在金表面制备自组装单分子膜. Au-SMAP在铑催化的还原醇硅烷化反应中表现出很高的活性和转化效率.半空心三炔基膦配体的研究合成了不同封端基团的三炔基膦配体。具有大体积封端的那些显示出独特的配位性质，以形成1：1的金属膦配合物选择性地与各种过渡金属物种。在铑催化的酮硅氢加成反应中，半空心结构的三乙炔基膦表现出非常高的促进作用。此外，半空心的三乙炔基膦被成功地用作金催化的炔环化反应的配体。特别是在6-exo-dig和7-exo-dig环化反应中，促进效果显著。此外，该催化剂体系能够实现前所未有的内炔衍生物的环化。